Dis-and polyazo dyestuffs and a process of making same



Patented Oct. 20, 1953 UNITED STATES PATENT OFFICE DIS- AND rorz-Azo DYESTUFFS AND A rnocass OF MAKING SAME Oscar Knecht and Hans Ischer, Basel, Switzerland, assignors to Sandoz Limited, Basel, Switzerland, a Swiss No Drawing. Application June 26', 1950, serial No. 170,460. In Switzerland January 17, 1947 14 Claims. (Cl. 260159) This is a continuationdn-part of our copending patent application Ser. 2,123, filed on January 13, 1948.

The present invention relates to new and valuable disand polyazo dyestufis and to a process for their production. The new dyestuffs are obtained by treating acylamino azo dyestuffs of the formula 0H N'=NR R1N=N wherein R and R1 represent residues oi unsubstituted or substituted aryl or heterocyclic compounds, X stands for a member of the group consisting of hydrogen and SO3H, one or the Y's meaning hydrogen and the other Y being acyl and R meaning a member of the group consist-- ing of hydrogen, alkyl, cycloalkyl, aralkyl, aryl and acyl, with saponifyingagents in order to convert the N group into N acyl The azo dyestuffs used as starting material may be prepared for instance in the manner described in the aforesaid co'pending application (acylamino-disand polyazo dyestuffs). Thus, these starting dyestuffs may be prepared by coupling any desireddiazo compound in an acid medium with an hydroxy-acyl-amino azo-dyestuil obtained by treating withan acylating agent are, dyestuffs of the'formula on N=N-R v wherein R. has the precedingly-indicated signiaryl, and treating subsequently with saponi- Tying agents to split off the acyl residue attached beingby weight:

ficance, :1: stands for a member of the group-consisting of hydrogen and --SO3H and one of the ys means hydrogen and the other -NIIR,, R

representing a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, aralkyl 'The saponification may treatment with saponifyingagents such as sodium carbonate, ammonia, sodium hydroxide, barium hydroxide, acetic acid or mineral acids at ordinary or at elevated temperatures. I1 the new dyestuffs contain groups being capable of forming complex metal compounds they can be treated in substance or on fibres with metal-yielding agents such as chromium acetate, copper sulfate and the like. According to the nature of the residue R and R1 the new dyestufi's can be 1 used for dyeing animal, vegetable or synthetic fibres or leather, whereby shades of good lastness properties to light and to washing and in --some-- cases. of good fastness properties to milling are obtained.

The following examples, without being limitatiye, illustratethe present invention, the parts 7 Example 1 70.8 parts of the disazo dyestufl."

0H =NONm NH-C O CH:

are heated a 'soo c; for a short time ina.1.%

sodium hydroxide solution. After neutralizing the amino-disazo dyestufi is salted out, filtered off and dried at 90 C. The thus obtained primary disazo dyestuff of the formula 3 is a dark powder dyeing wool from an acid bath in deep brown shades of good fastness to light and excellent fastness to perspiration and to washing.

Example 2 72 parts of the acetylaminodisazo dyestufi OH MG 0.

are dissolved in a. 10% sodium carbonate solu- OH IIT=N SOaH Example 3 is dissolved in 2000 parts of a sodium carbonate solution and heated for 5 to 7 hours at 90 C. until the acetylamino group being attached to the naphthalene nucleus is split off. Then Example 4 116 parts of the copper complex compound oi.

NHCOCH: vOHiCOHN are dissolved in 1200 parts of a 5% sodium carbonate solution and boiled for 4 hours. When the acetylamino group is saponified to NH: the new dyestufi is salted out with 120 parts of sodium chloride, filtered off and dried. The new dyestufl, a dark powder, dyes cotton in violet brown shades of good fastness to light.

The corresponding uncoppered dyestufl dyes leather in deep dark brown shades possessing, when after-chromed, an excellent fastness to light, to washing and to brushing.

Example 5 120 parts of the diacetylamino-tetrakisazo dyestufl 301E BIOsH are dissolved in 2500 parts of a 10% sodium carbonate solution and heated for 5 hours at 90 C. When the saponification of the two acetylamino groups is finished, the new dyestufi is precipitated by adding 250 parts of sodium chloride,

35 filtered off and dried. It dyes wool and cotton I 85 parts of the polyazo dyestufi in fast grey shades.

coon on N=N Nnooorn noON=N- N=N NH0 0 011.

Example 6 60 parts of the acetylamino disazo dyestufl' NHC 00133 are warmed for a short time in a 5% barium hydroxide solution to C. When the hydrolysis is complete, the solution is cooled to room temperature and the precipitated aminoazo dyestufi filtered 0E and the barium salt converted in the the polyazo dyestuff usual manner into the sodium salt. The thus OH on N=N- son:

on on N=N No, 0311 N: -OON=N nnooom obtained new azo dyestufi is a. dark powder dye-.- ing wool from an acid bath in brown violet shades of very good fastness to light and to washing.

The new dyestufi containing a primary amino group can further be, diazotized and coupled with "age heated for one hour in a 5 to 10% barium hydroxide solution at 80 After cooling to 40 C. the dyestufi is filtered ofi and converted into the sodiums alt The thus obtained aminoazo dyestuff dyes wool and cotton in dark brown 5 ggplillg-ggmggggts shades. The dyestuff may further be diazotized Ewampl 7 and coupled with coupling components.

The nventio i further z luaira-t d by h 90 parts of the acetylamino azo dycstuff ierent examples given in the following tables.

COOH OH N-,=N

OaH

HG 06H:

91 m compound II 0. l

NH-acyl Dia c pmpo dll 1101a- Shadeonwsmi Diazo compound I Acyl Diazo compound II Dyestufl with Dyestufl with NH.acyl Nil:

Orthaniiic acid Acetyl; Orthanilicacid Rcd Brown-olive.

A Bcnzoyi d ..-do Do.

-p.-.Io1i1ene-. Do.

sulfonyl.

Acetyl 5-.aeetylaminmZ-aminobcnzened=sulfonic acid-",1", Brown.

4(4-amiuo-1-benzoylamino)-l-hydroxy:2 henzoic acid Reddish brown. 4,4-amino-azo-benzcne-sulfonic acid Dark-brown. Orthanilic acid Do. 4-(iQamino-Y-benzoylamino)-1-hydroxy-2-benzoica v Brown-red. Arming.-. Rcddishbmwn. Sulfamhc acid Brown-red. Metanilic i Do.

, 4-(4 amino-1-benzoylamino)-1-hydroxy-2-benzoic acid D Aniline 1 H Bed-brown.

ionic acid 14 do Metanilic acid D SuIfafiiIic d Do.

3-11i trnanih:nn Bmwn-r d, 4-n t zoanillnen Brownii're. iammo-azo-benz Dark-brown. Monoazo dyestufi' Violet-grey Do.

sulfonic acid. Sulianilic c Blue-red Brown-Orange. Naphthiomc acid. BIOWIi-Xl0le.t--.-.- Orange-taxman. Aniline Yellow-brown... Red-brown.

4-ch1oro-ani1ine Do. 24 do Orthanilic acid, Brown.

droxy-3-su1fobenzoic acid. 25 -do .d0. 0 q-fi j Brown-red Do. 26;"..- 6-acetyiamino-2- .d0 Orthamllc acid I an Browwolive.

aminobenzenel-sulfonic acid. I

Naphthiomc acid- Brown-violet.-. Black-brown. l-naphthyla nm I Do. s-aoetylamino-z-aqlinobenzone-l-sultonic acid" Red Brown-olive. 4-(4-amino-i-bengoy1ammo)-1-hydroxy-2-benzoic acid" Brownish-red... Dark-brown. 4.4amino-azp-benaene-sulfonio acid Blue-rein..." Do. Monoazo dyestufi: aniline 1.7-naphthylamine- Grey-violet..." D0.

Naphthipnic acid s ilfolnyl.

suifonic acid. Orthanilic acid Sulfaniiic acid- Napithionic acid 5-acetylamino-Z-aminobenzone-l-sulfonic acid Monoazo dyestutf: aniline III-naphthyla sulionic acid.

l-naphthylamine Tetrazo compound of 4.4"-diaminobenzaniiide Intermediate product made from 4.4'-tetrizodiphelnyl+ 1 mol salicylic acid. Intermediate product made from 4;.

39! 4 ?l QPl?6 YDr3'm hy Intermediate product "made y 1 mol 1-(4-suifopheny1)-5-pyrazol y Intermediate product made from 4.4-tctrazodiphei1yl+ 1 mol acetoacetanilide.

shade o'n' co t IBrown-red edeem... I

Reddish-btown Red-brownv Black-brown. Dark-brown. Black-bifown.

D0. Brown. Black-bigoWn.

ishbrown.

TABLE 1-Continued Shade on wool Diazo compound I Acyl Diazo compound II Dyestufl'. with Dyestufi with Nllacyl NH:

47.1."- 5-8mi 0- Y- fi y Intermediate product made from 4.4-tetrazod.iphenyl+ Reddish-brcwm. Brown.

- droxy-3-eulfd 1 mol salicylic acid.

benzoic acid. 48 5-acetylamino-2- do. O N=N B1uish-grey. Grey.

amino-benzenel-sulfonic acid.

' 503E soui 49-- d0--.--.-- .d0-..- Intermediate product made from 4.4'-tetrazodiphenyl+ Brown-violet--. Yellowish-brown.

1 mol salicylic acid. 50 5-acetylamm0-2- d0 Intermediate product made from 4.4-tetrazobenzanilide+ Violetbr0w'n-- Do.

amlno-lpen cn 1 mol salicylic acid. l-sulfomc acid. 61 do d0-- Intermediate product-made from 4.4'-tetrazodiphenyl+ Brown D0.

1 mol 1- (4'-sulio-phenyl)-3-methyl-5-pyrazoloue. 52 5-nitro-2amin r do- N=N Blue-grey Grey.

benzene-l-sulionic acid.

- 7 1 803B 50:11 53 do do- Intermediate product made from 4.4'- tetrazodiphenyl-l- Violet-brown-.. Yellowishbrown.

1 mol salicylic acid. 54 do do Intermediate product made from 4.4-tetrazodiphenyl+ Red-brown D0.

1 mol 1-(4"sulfopheny1)-3-methyl-5-pyrazol'0ne. 65 do .dc. Intermediate product made from 4.4-tetrazodiphenyl+ Brown-violet--. Dark-brown.

1 mol 1-(4-sulfophenyl)-5-pyrazo1onc-3-carboxylic acid. 56"-.-- .do .do. Intermediate product made from 4.4-tetrazodiphenyl+ do Violet-brown. 1 mol of the metalliferous dyestufl.

HO 00u0 I I, r =N -s0 H 57---.-- do do Intermediate product made from 4.4- tetrazodiphenyl+ Violet-brown Yellcwish-brown.

1 mol o-cresotic acid. 58---... do do Intermediate product made from 4.4-tetrazodiphenyl+ Red-brown Brown.

1 mol phenol.

salicylic acid 59-- d do. Benzidinc Greenish-black- Dark-brown.

LT-naphthyl-aminesulfonic acid 60 do do Intermediate product made from 4.4-tetrazobenzanilide+ Violet-brown-.. Yellowish-brown.

1 mol salicylic acid.

61 5-acetylamin0-2- do CHJO N=N Nz.Cl Brown-violet--. Brown.

aminobenzenel-sulfonic acid.

810 011: 62 Sulfanilic mm on Brown Do.

TABLE 2 Diazo compound I 0.. l

Diazo compound H ---i Nfllacyl Shade on Wool Diazo compound I Acyl residue Diazo compound II Dyestufi with Dyestufi with NH.acyl NH:

1 5-nitro-2-amino- Acetyl l-naphthylamlnn Violet Dark-brown.

benzene-l-sulionic acid. 2 do do Naphthionic acid V D0- 3' Z-aminonaphtha- -do Anilin Red Violet-brown lene-c-sulionic acid. 4 do do -chloro-aniline d Greyish-brown. 6 Z-aminonaphtha- ....-do Intermediate product made from 4.4 Brownish-red. ar r wnleuie-Ersulfonic 1 mol salicylic acid. an

a What we cla m is; wherein R1 stands for the radical or a compound '1 An no dvestufic: the ionnulel selected from the group consisting of benzene, 0E N -N l naphthalene and :pyranolone compounds containing at most two azo groups, and Z stands tor-a 5 member selected from the'group consisting of hydrogen, halogen, --NH-acy1, 'NO:; and

SOsI-L I 3; An azo' dyestuff of the formula scar 4. An azo dyestufi of the formula g I I 00011 on N=NON11coom HOON=N e -N=N 7 NH:

SOIH v i 5. An azo dyestuff of the formula HtnN N i I 6. An azo dyestufi of the formula COOH HO N=- N wherein R represents a radical selected from the 7. An azo dyestufi? of the-1 mm group consisting of a phenyl radical containing a -SO3H group in ortho-position to the adja- 016B: OH N=N cent azo group and a naphthyl radical containing a -SO3H group in ortho-position to the N=N adjacent azo group, R1 stands for the radical of 0 v a compound selected from the group consisting 03 of benzene, naphthalene and pyrazolone compounds containing at most two azo groups, X A procefss for m i re of an azo stands for a member selected from the group dyetum whlch comprises the eps of coupling consisting of hydrogen and SOsH, one of the Y's dlazo compound Selected from h roup conbeing hydrogen and the other Y being NHa. sisting of benzene Paphthalene and :PS' aZOIOne 2. An azo dyestufi of the formula 3 compwnds Wlth an 320 y st fi of the for- SOaH m a Z on N=N-R OH N=N R1-N=N NH! BOIH- wherein R stands for the radical of a compound selected from the class consisting of compounds of the benzene and naphthalene series, :1: stands for a member of the group consisting of hydrogen and -SO3H, one of the ys being hydrogen and the other 1! being an acylated NHz group, and then treating the coupling product with a saponifying agent, whereby the acylated NHa group is converted into NH2.

9. A process for the manufacture of an azo dyestufi, which comprises the steps of coupling a diazo compound of the benzene series with an azo dyestuff of the formula 7 OH N=NR NELacyl HOzS wherein R stands for the radical of a compound of the benzene series, and then treating the coupling product with a saponifying agent, whereby the -NH.acyl group is converted into -NH2.

10. A process for the manufacture of an azo dyestufi, which comprises the steps of coupling a diazo compound of the naphthalene series with an azo dyestufi of the formula wherein R stands for the radical of a compound of the benzene series, and then treating the coupling product with a saponifying agent, whereby the -NH.acyl group is converted into -NH=.

11. A process for the manufacture of an azo dyestufi, which comprises the steps of coupling 7 a diazo compound of the pyrazolone series with an azo dyestuff of the formula 0H N=N-R NHncyI 0H N=N NHCOCE 12 wherein Z stands for a member of the group consisting of hydrogen-halogen, NH.acyl, -NO: and SO3H, and then treating the coupling product with an alkaline saponifying agent, whereby the NHCOCI-l's group on the naphthalene nucleus is converted into NH2.

13. A process for the manufacture of an azo dyestuff, which comprises the steps of coupling a diazo compound of the naphthalene series with an azo dyestufi' of the formula SOaH OH N=N- -NH0 0 03a HOaS wherein Z stands for a member of the group consisting of hydrogen, halogen, NH.acyl, NO: and SOsI-I, and then treating the coupling product with an alkaline saponifying agent, whereby the --NHCOCH3 group on the naphthalene nucleus is converted into NH2.

14. A process for the manufacture of an azo dyestufi, which comprises the steps of coupling a diazo compound of the pyrazolone series with an azo dyestufi of the formula SOaH OH N=N NHC OCH:

wherein Z stands for a member of the group consisting of hydrogen, halogen, NH.acyl, NO2 and SO3H, and then treating the coupling product with an alkaline saponifying agent, whereby the -NHCOCH3 group on the naphthalene nucleus is converted into -NH2.

OSCAR KNECHT.

HANS ISCHER.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,192,153 Ross Feb. 27, 1940 2,553,261 Knecht et a1 May 15, 1951 

5. AN AZO DYESTUFF OF THE FORMULA 